JP5029363B2 - 強誘電体層付き基体の製造方法 - Google Patents
強誘電体層付き基体の製造方法 Download PDFInfo
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Description
工程A:ガラスマトリックス中でPbxLa1−xZryTi1−yO3(0.5≦x≦1、0≦y<0.4)の結晶性微粒子を形成した後、ガラスマトリックス成分を除去して該結晶性微粒子を得る工程。
工程B:工程Aで得られた結晶性微粒子と、加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と、液状媒体とを含んでなり、前記結晶性微粒子と前記可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜70/30である流動性組成物を基体上に塗布し、200〜500℃で加熱して第1の層を形成する工程。
工程C:前記可溶性金属化合物と、液状媒体とを含み、前記結晶性微粒子を実質的に含まない流動性組成物を前記第1の層上に塗布し、200〜500℃で加熱して第2の層を形成する工程。
工程D:前記第1の層と第2の層とが形成された基体を、500℃超〜700℃の温度で焼成する工程。
2:上部電極
3:強誘電体層
4:下部電極
5:プラグ
6:ソース電極
7:ソース
8:ワード線
9:ゲート電極
10:ゲート絶縁膜
11:ドレイン
12:ドレイン電極
13:ビット線
14:半導体基板
15:層間絶縁膜
16:第1の層
17:第2の層
〔1〕ガラス形成成分(例えば、酸化ホウ素)と、目的とする強誘電体酸化物組成の金属酸化物(例えば、酸化ジルコニウム、酸化チタン及び酸化鉛)とを混合し、1200℃以上の温度で全体を溶融させる[溶融]。
〔2〕溶融ガラスを急速冷却させることによって強誘電体酸化物組成の金属イオンを含むガラスを得る[ガラス化]。
〔3〕550℃〜700℃程度の温度でアニール処理を行うことでガラス中に強誘電体酸化物の結晶核を形成させ、アニール条件を制御して所定の粒子径まで成長させる[結晶化]。
〔4〕酸、水、あるいはその混合物によりガラス母材成分(例えば、酸化ホウ素)を取り除き結晶性の強誘電体微粒子(例えば、Pb(ZryTi1−y)O3)を得る[リーチング]。
工程B:工程Aで得られた結晶性微粒子と、加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と、液状媒体とを含んでなり、前記結晶性微粒子と前記可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜70/30である流動性組成物を基体上に塗布し、200〜500℃で加熱して第1の層を形成する工程。
工程C:前記可溶性金属化合物と、液状媒体とを含み、前記結晶性微粒子を実質的に含まない流動性組成物を前記第1の層上に塗布し、200〜500℃で加熱して第2の層を形成する工程。
工程D:前記第1の層と第2の層とが形成された基体を、500℃超〜700℃の温度で焼成する工程。
酸化鉛、酸化チタン(ルチル)及び酸化ホウ素を、PbO、TiO2及びB2O3としてそれぞれ47.2モル%、25.0モル%及び27.8モル%含むように秤量し、エタノール少量を用いて自動乳鉢でよく湿式混合した後乾燥させて原料粉末とした。得られた原料粉末を、融液滴下用のノズルのついた白金製容器(ロジウム10%含有)に充填し、ケイ化モリブデンを発熱体とした電気炉において1350℃で2時間加熱し、完全に溶融させた。次いでノズル部を加熱し、融液を電気炉の下に設置された双ロール(ロール径150mm、ロール回転数50rpm、ロール表面温度30℃)に滴下しフレーク状固形物を得た。
上記で得られた分散液A及び溶液Bを、Pb比で3:97となるように混合し、固形分が10質量%となるように調整した液をスピンコート液Dとして使用した以外は例1と同様にして第1の層(層厚:160nm)を得た。次に、第1の層上に、例1と同様にして第2の層を積層し、例1と同様に焼成して強誘電体層を得た。強誘電体層の層厚は200nmであった。
Pt電極付きSi基体上に、溶液Bのみを3000rpmで20秒間、スピンコートした。その後、120℃、350℃で各10分間加熱し、乾燥させた。この塗布−乾燥からなる工程を4回繰り返したのち、横型酸化炉を用いて、酸素雰囲気中650℃の条件で60分間焼成して強誘電体層を得た。得られた強誘電体層の層厚は200nmであった。
例1〜3で得られた強誘電体層上に300μm角のAu薄膜からなる上部電極2を真空蒸着法で形成し、RTA炉にて500℃で、5分間のポストアニール処理を行って誘電特性の評価用試料とした。なお、ヒステリシス測定及びリーク電流測定は、東陽テクニカ製のFCE−1を用いて測定した。
表1に6Vの三角波を入れた時の最大分極値及び残留分極値を示し、表2に3V印加時及び6V印加時のリーク電流特性を示す。
上記で得られたスピンコート液Cを、Pt電極付きSi基体上に3000rpmで20秒間、スピンコートした後、120℃、350℃で各10分間加熱し、乾燥させて第1の層(層厚:50nm)を作製した。
焼成温度を700℃に変更した以外は例4と同様にして、強誘電体層3(層厚:200nm)を得た。
焼成温度を600℃に変更した以外は例3と同様にして、強誘電体層(層厚:200nm)を得た。
焼成温度を700℃に変更した以外は例3と同様にして、強誘電体層(層厚:200nm)を得た。
例4〜7で得られた強誘電体層の表面を、走査型電子顕微鏡(日本電子株式会社製、商品名:JSM−6340F)により観察した結果をそれぞれ図6〜9に示す。
酢酸鉛、テトラブチルチタネート、テトラブチルジルコネート及びアセチルアセトンを、2−エトキシプロパノール中にPb:Zr:Ti:アセチルアセトン=1.05:0.60:0.40:1.00(モル比)となるよう溶解させ、窒素気流中130℃で4時間の還流操作を行った。この溶液を室温まで冷却し、イオン交換水を(Pb+Zr+Ti)の2倍(モル比)となるようゆっくりと添加した。その後、再度窒素気流中130℃で8時間の還流加熱を行い、α−テルピネオールを加えて可溶性金属化合物溶液Eを得た。このとき、金属源の液中濃度は、酸化物換算で20質量%とした。
Pt電極付きSi基体上に、溶液Eのみを1000rpmで20秒間、スピンコートした。その後、120℃、350℃で各10分間乾燥させた。この塗布−乾燥からなる工程を4回繰り返した。こののち、横型酸化炉を用いて、酸素雰囲気中650℃の条件で60分間焼成して強誘電体層を得た。得られた強誘電体層の層厚は0.6μmであった。
例8、9で得られた強誘電体層上にφ1mmのアルミニウム薄膜からなる上部電極2を真空蒸着法で形成し、上記と同様のポストアニール処理を行って誘電特性の評価用試料とした。なお、リーク電流測定はKeithley社製のソースメーター6430を用いて行い、比誘電率測定は、日置電気社製のLCR Hi Tester3532−50を用いて行った。
表4に強誘電体層中のクラックの有無、10V印加時のリーク電流特性及び1kHzにおける比誘電率を示す。
本出願は、2005年8月19日出願の日本特許出願(特願2005−238816)、2006年5月17日出願の日本特許出願(特願2006−137913)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (8)
- 平均一次粒子径が20〜300nmであるPbxLa1−xZryTi1−yO3(0.5≦x≦1、0≦y<0.4)の結晶性微粒子と、加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と、液状媒体とを含んでなり、前記結晶性微粒子と前記可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜70/30である流動性組成物を基体上に塗布し、液状媒体を除去した後500℃超〜700℃の温度で加熱することを特徴とする強誘電体層の製造方法。
- 平均一次粒子径が20〜300nmであるPbxLa1−xZryTi1−yO3(0.5≦x≦1、0≦y<0.4)の結晶性微粒子と、加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と、液状媒体とを含んでなり、前記結晶性微粒子と前記可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜70/30である流動性組成物を基体上に塗布し、液状媒体を除去して前記結晶性微粒子を含む第1の層を形成し、次いで加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と液状媒体とを含みかつ前記結晶性微粒子を実質的に含まない第2の流動性組成物を前記第1の層上に塗布し、液状媒体を除去して第2の層を形成し、その後500℃超〜700℃の温度で加熱することを特徴とする強誘電体層の製造方法。
- 前記結晶性微粒子が、ガラスマトリックス中でPbxLa1−xZryTi1−yO3(0.5≦x≦1、0≦y<0.4)の結晶性微粒子を形成した後、ガラスマトリックス成分を除去して得られた結晶性微粒子である、請求項1又は2に記載の強誘電体層の製造方法。
- 前記結晶性微粒子の平均一次粒子径が20〜100nmであり、流動性組成物中の結晶性微粒子と可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜30/70であり、かつ、得られた強誘電体層の層厚が80〜300nmである請求項1、2又は3に記載の強誘電体層の製造方法。
- 前記結晶性微粒子の平均一次粒子径が30〜300nmであり、流動性組成物中の結晶性微粒子と可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=20/80〜70/30であり、かつ、得られた強誘電体層の層厚が0.5〜10μmである請求項1、2又は3に記載の強誘電体層の製造方法。
- 下記工程A〜Dを含むことを特徴とする強誘電体層付き基体の製造方法。
工程A:ガラスマトリックス中でPbxLa1−xZryTi1−yO3(0.5≦x≦1、0≦y<0.4)の結晶性微粒子を形成した後、ガラスマトリックス成分を除去して該結晶性微粒子を得る工程。
工程B:工程Aで得られた結晶性微粒子と、加熱によりPbxLa1−xZryTi1−yO3(0.5≦x≦1、0.4≦y≦0.7)を形成する可溶性金属化合物と、液状媒体とを含んでなり、前記結晶性微粒子と前記可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜70/30である流動性組成物を基体上に塗布し、200〜500℃で加熱して第1の層を形成する工程。
工程C:前記可溶性金属化合物と、液状媒体とを含み、前記結晶性微粒子を実質的に含まない流動性組成物を前記第1の層上に塗布し、200〜500℃で加熱して第2の層を形成する工程。
工程D:前記第1の層と第2の層とが形成された基体を、500℃超〜700℃の温度で焼成する工程。 - 前記結晶性微粒子の平均一次粒子径が20〜100nmであり、前記工程Bにおける流動性組成物中の結晶性微粒子と可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=5/95〜30/70であり、かつ、得られた強誘電体層の層厚が80〜300nmである請求項6に記載の強誘電体層付き基体の製造方法。
- 前記結晶性微粒子の平均一次粒子径が20〜300nmであり、前記工程Bにおける流動性組成物中の結晶性微粒子と可溶性金属化合物との含有比率が、Pb比で[結晶性微粒子]/[可溶性金属化合物]=20/80〜70/30であり、かつ、得られた強誘電体層の層厚が0.5〜10μmである請求項6に記載の強誘電体層付き基体の製造方法。
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